| 2721789 | Hydrogen generator | Gill | 23/282 | |
| 3348919 | Process for producing hydrogen from finely divided metals and water at ambient temperatures | Shumway | 23/211 | |
| 3554707 | Holmes | 23/282 | ||
| 3942511 | Sandwiched structure for production of heat and hydrogen gas | Black et al. | 126/248 | |
| 3957483 | Magnesium composites and mixtures for hydrogen generation and method for manufacture thereof | Suzuki | 75/.5R | |
| 3975913 | Gas generator and enhanced energy conversion systems | Erickson | 60/645 | |
| 4223661 | Portable diver heat generating system | Sergev et al. | 126/204 | |
| 4269818 | Method of producing hydrogen | Suzuki | 423/657 | |
| 4340580 | Method of producing hydrogen | Suzuki | 423/657 | |
| 4598552 | Energy source for closed cycle engine | Weber | 60/673 | |
| 4643166 | Steam engine reaction chamber, fuel composition therefore, and method of making and operating same | Hubele et al. | 126/263 | |
| 4670018 | High BTU fuel element | Cornwell | 44/1E | |
| 4730601 | Steam engine reaction chamber, fuel composition therefore, and method of making and operating same | Hubele et al. | 126/263 | |
| 4752463 | Method of producing hydrogen and material used therefor | Nagira et al. | 423/657 | |
| 4769044 | High BTU fuel element | Cornwell | 44/605 | |
| 4882128 | Pressure and temperature reaction vessel, method, and apparatus | Hukvari et al. | 422/119 | |
| 5143047 | Material and method for fast generation of hydrogen gas and steam | Lee | 126/263 | |
| 5286473 | Process for the production of hydrogen | Hasebe | 423/657 | |
| 5833934 | Demand responsive hydrogen generator based on hydride water reaction | Adlhart | 422/239 | |
| 5867978 | System for generating hydrogen | Klanchar et al. | 60/39.182 | |
| 6506360 | Method for producing hydrogen | Andersen et al. | 423/657 |
| CA2116468 | ||||
| CA2225978 | ||||
| DE2436002 | ||||
| DE3401194 | ||||
| EP0312078 | Apparatus for chemically generating and dispersing gas. | |||
| FR2465683 | ||||
| JP401208301 | ||||
| WO/1994/018117 | PROCESS FOR THE PRODUCTION OF HYDROGEN |
This invention relates to the production of hydrogen gas from the reaction of aluminum with water in the presence of sodium hydroxide as catalyst.
Hydrogen energy is environment-friendly. Because of the actual human ecology concerns, the exploitation of hydrogen as an universal fuel would be greatly acclaimed. During the last two decades or so, the elaboration of a hydrogen-based economy has made important progress on account of numerous research projects such as the hydrogen fuel cell and the hydrogen car. Although these important discoveries constitute milestones toward a pollution-free society, more research is needed to obtain the hydrogen easily and economically.
A convenient source of hydrogen is a reaction of aluminum with water to split the water molecules into hydrogen and oxygen. The hydrogen is released as a gas and the oxygen combines with the aluminum to form aluminum oxide compounds. Aluminum is the third most abundant element after oxygen and silicon in the earth's crust, and constitutes approximately 8% by weight of the earth's crust. Aluminum is a safe material and is commonly used in the food, cosmetics and medical fields. Water is also abundant. Therefore, the reaction of these two elements to produce hydrogen represents an interesting proposal to replace fossil fuels.
Generally speaking, it is known that under certain conditions, aluminum reacts with water to generate hydrogen and heat. It is also known, however, that this type of reaction is not sustainable at ambient temperature. It is believed that a protective oxide layer forms on a metal surface in contact with water at ambient temperature and hinders the reaction. Therefore, it has been accepted by those skilled in the art that the use of aluminum in a reaction with water to generate hydrogen gas requires that the protective oxide layer is efficiently and continuously removed, and that the reaction is kept at an elevated temperature.
A number of hydrogen generators have been developed in the past. The following patent documents constitute a good inventory of the devices and methods of the prior art in the field of hydrogen gas generation using the reaction of aluminum or alloys of aluminum with water.
U.S. Pat. No. 909,536 issued on Jan. 12, 1909, and U.S. Pat. No. 934,036 issued on Sep. 14, 1909, both issued to G. F. Brindley et al. These documents disclose several compositions for generating hydrogen. The compositions comprise any metal which can form an hydroxide when it is brought into contact with a solution of a suitable hydroxide. For example, aluminum is reacted with sodium hydroxide to release hydrogen and to produce sodium aluminate.
U.S. Pat. No. 2,721,789, issued on Oct. 25, 1955 to Q. C. Gill. This document discloses the structure of an hydrogen generator for reacting water with a measured dry charge of aluminum particles and flakes of sodium hydroxide. The reaction releases hydrogen gas and produces sodium aluminate.
U.S. Pat. No. 3,554,707 issued on Jan. 12, 1971 to W. A. Holmes et al. This document discloses a gas generator having bellows to raise or lower the level of water in response to the pressure inside the generator. As the level of water drops, the contact surface between the fuel cartridge and the water is lost and the reaction is terminated.
U.S. Pat. No. 3,957,483 issued on May 18, 1976 to M. Suzuki. This patent discloses a magnesium composition which produces hydrogen upon contact with water. The preferred magnesium composition comprises magnesium, and one or more metals selected from the group consisting of iron, zinc, chromium, aluminum and manganese.
U.S. Pat. No. 3,975,913 issued on Aug. 24, 1976 to D. C. Erickson. This document discloses a hydrogen generator wherein molten aluminum is reacted with water. The generator is kept at a very high temperature to keep the metal in a molten condition.
U.S. Pat. No. 4,643,166 issued on Feb. 17, 1987, and
U.S. Pat. No. 4,730,601 issued on Mar. 15, 1988 both to H. D. Hubele et al. These documents disclose the structure of a fuel cell for producing heat energy and hydrogen gas. The device has a reaction chamber containing a fuel composition that is reactive with water. The fuel composition includes a main fuel part of magnesium and aluminum in a molar ratio of 1:2, and the second part is composed of lithium hydride, magnesium and aluminum in equal molar ratio.
U.S. Pat. No. 4,670,018 issued on Jun. 2, 1987, and
U.S. Pat. No. 4,769,044 issued on Sep. 6, 1988, both to J. H. Cornwell. These documents describe a log made of compressed wood waste and paper. The log is coated with aluminum particles. Upon burning, the aluminum particles react with moisture in the log to emit heat due to the generation of hydrogen gas.
U.S. Pat. No. 4,752,463 issued on Jun. 21, 1988 to K. Nagira et al. This document discloses an alloy which reacts with water for producing hydrogen gas. The alloy material comprises essentially aluminum and 5 to 50% tin.
U.S. Pat. No. 5,143,047 issued on Sep. 1, 1992 to W. W. Lee. This document discloses an apparatus and a method for generating steam and hydrogen gas. In this apparatus, an aluminum or aluminum alloy powder is reacted with water to generate hydrogen gas. An electric power source is used to start the reaction. The electric power source is used to explode an aluminum conductor and to disperse pieces of molten aluminum into a mixture of water and aluminum powder. A heat exchanger is provided to extract useful heat.
U.S. Pat. No. 5,867,978 issued on Feb. 9, 1999 to M. Klanchar et al. This document discloses another hydrogen gas generator using a charge of fuel selected from the group consisting of lithium, alloys of lithium and aluminum. The charge of fuel is molten and mixed with water to generate hydrogen gas.
JP 401,208,30 issued to Mito on Aug. 22, 1989. This document discloses a process for producing hydrogen. Aluminum is reacted with water under an inactive gas or a vacuum to produce hydrogen gas.
CA 2,225,978 published on Jun. 29, 1999 by J. H. Checketts. This patent application discloses a hydrogen generation system wherein a coating on reactive pellets is selectively removed to expose the reactive material to water for producing hydrogen gas on demand. In one embodiment, aluminum and sodium hydroxide are reacted with water to release hydrogen gas and produce sodium aluminate.
DE 3,401,194 published in Jul. 18, 1985 by Werner Schweikert. This document discloses a device for utilizing energy from a chemical reaction between various aluminum alloys and sodium hydroxide. The chemical reaction occurring in this device generates heat, hydrogen gas, a direct current and sodium aluminate as a residue.
FR 2,465,683 published in Mar. 27, 1981 by Guy Ecolasse. This document also discloses a process for producing hydrogen by the reaction of aluminum on sodium hydroxide solution in water. A by-product of this reaction is sodium aluminate.
Belitskus, David. 1970. Technical Note: “Reaction of Aluminum With Sodium Hydroxide Solution as a Source of Hydrogen” J. Electrochem Soc. (1970), (August), Vol. 117. No. 8, pp.1097-9, XP-002180270. This technical paper.describes several experiments wherein aluminum samples including a cylindrical block, uncompacted powders and pellets of various densities have been reacted with aqueous solutions of sodium hydroxide at various concentrations to generate hydrogen gas. In these experiments, the formation of sodium aluminate was observed, as well as the regeneration of sodium hydroxide through the precipitation of aluminum hydroxide.
Stockburger, D. et al. 1991. “On-Line Hydrogen Generation from Aluminum in an Alkaline Solution”. Proc.-Electrochem. Soc. (1992), Vol. 92-5 (Proc. Symp. Hydrogen Storage Mater., Batteries, Electrochem., pp. 431-44, 1992, XP-001032928. This technical paper describes three sizes of hydrogen generators in which aluminum is reacted with an aqueous solution of 5.75 M sodium hydroxide. This technical paper also notes the formation of sodium aluminate and the precipitation of aluminum hydroxide that regenerates sodium hydroxide.
Although the chemical reactions of aluminum with water in the presence of sodium hydroxide have been demonstrated in various projects in the past, these reactions were not considered as being safe for use by the general public. Sodium hydroxide is extremely corrosive and must be handled according to particular safety procedures. Therefore, any chemical reaction wherein sodium hydroxide is a consumable would not represent an attractive source of hydrogen for use in vehicles or in household power systems, for examples. As such, it is believed that a need still exists for a method to produce hydrogen gas by the reaction of aluminum and water, wherein the consumables are limited to aluminum and water.
Broadly stated, the process for producing hydrogen gas according to the present invention consists of reacting aluminum with water in the presence of sodium hydroxide acting as a catalyst.
In accordance with one aspect of the present invention, there is provided a process for producing hydrogen gas, comprising the initial step of: providing an aqueous solution in a vessel. The aqueous solution contains sodium hydroxide in a concentration between 0.26 M and 19 M NaOH.
The next step consists of reacting aluminum with water at the surface of the solution thereby generating a region of effervescence at the surface of the solution and a precipitate sinking to the bottom region of the vessel. The process also includes the step of maintaining the region of effervescence separated from the precipitate at the bottom the vessel, to prevent the precipitate from swirling and mixing with the aluminum in the reaction zone at the surface of the solution. This process is advantageous because it proceeds catalytically with the sodium hydroxide acting as the catalyst.
The process mentioned above is best carried out with an aqueous solution containing between about 5M and 10 M NaOH. The process is also more efficient when makeup water is added only after an initial amount of aluminum has been consumed, and when the temperature of the aqueous solution has reached a peak or 75° C.
In accordance with another aspect of the present invention, there is provided a process for initiating and maintaining a catalytic reaction of aluminum with water for producing hydrogen gas. The process comprises the initial step of providing an aqueous solution in a vessel. This aqueous solution contains a portion of NaOH and a portion of water. The next steps consist of introducing a portion of aluminum in the aqueous solution, and reacting that portion of aluminum with the portion of water. The process also includes the steps of maintaining constant the portion of NaOH in the vessel and adding additional portions of water and additional portions of aluminum in the vessel according to the rates of consumption of the aluminum and the water in the reaction.
Again, this process is best carried out with an aqueous solution of between 1.2 M and 19 M NaOH and at a temperature between 4° C. and 170° C.
In yet another aspect of the present invention, there is provided a process for simultaneously producing hydrogen gas and alumina (Al
Other advantages and novel features of the present invention will become apparent from the following detailed description,.
A preferred embodiment of the process according to the present invention selected by way of examples will now be described with reference to the accompanying drawings, in which:
In the present invention it is believed that aluminum reacts with water under certain conditions in the presence of sodium hydroxide as a catalyst. It is believed that the reaction is carried out according to the equation (1) or possibly (2), or some combination of the two, as follows;
In one of the most pertinent prior art documents, the U.S. Pat. No. 934,036, it is taught that aluminum reacts with water and sodium hydroxide according to one of the following formulas;
In other relevant prior art documents, Stockburger and Belitskus teach that aluminum reacts with an alkaline solution of NaOH and that NaOH is subsequently regenerated by the precipitation of Al(OH)
It is also taught in Stockburger, that an optimum concentration of the alkaline solution should be maintained at 5.75 M NaOH for an acceptable reaction rate, and in Belitskus that the rate of precipitation of Al(OH)
The following experiments were carried out to demonstrate that under certain conditions, the sodium hydroxide is not consumed in the reaction but acts as a catalyst to the reaction as described in equation (1) or (2).
A first series of eight experiments was carried out to measure the volume of hydrogen gas produced in a typical reaction. In these experiments, aluminum foil from Reynolds Aluminum Company of Canada was loosely crumpled and placed in a one liter plastic bottle containing 500 ml of catalytic solution of about 4.5M NaOH. The bottle was quickly capped with a cover fitted with a tube which led to an inverted volumetric cylinder filled with water. The bottle was immersed in a water bath to prevent overheating.
The volume of water displaced by the gas produced was measured and corrected to a gas volume at standard temperature and pressure (STP). Atmospheric pressure on that day was obtained from a local weather office. The corrected volume of gas produced was compared to the theoretical quantity of hydrogen gas, which would be obtained according to the equation,
These experiments were carried out at a room temperature of 21° C. and an atmospheric pressure of 758 mm of Hg. In all cases the reaction started in few seconds and continued for few minutes, until depletion of the aluminum foil. It was noticed that a typical reaction with less than 5 grams of loosely crumpled aluminum foil, is complete in less than 5 minutes. The results of these experiments are shown in Table 1 below.
| TABLE 1 | ||||||
| Hydrogen Gas Production from Aluminum Foil | ||||||
| Exp. | Al | H | H | H | Yield | Deviation |
| (#) | (g.) | (l) | (STP) | Theoretical | (%) | (+/− %) |
| 1-1 | 2.08 | 2.94 | 2.71 | 2.59 | 104 | 2.6 |
| 1-2 | 2.03 | 2.85 | 2.62 | 2.53 | 104 | 2.6 |
| 1-3 | 2.21 | 3.05 | 2.81 | 2.75 | 102 | 2.5 |
| 1-4 | 2.16 | 2.9 | 2.67 | 2.69 | 99 | 2.6 |
| 1-5 | 2.2 | 3.04 | 2.8 | 2.74 | 102 | 2.5 |
| 1-6 | 2.21 | 3.04 | 2.8 | 2.76 | 102 | 2.5 |
| 1-7 | 0.73 | 1.03 | 0.94 | 0.91 | 103 | 2.4 |
| 1-8 | 0.83 | 1.15 | 1.05 | 1.03 | 102 | 2.2 |
| Ave. | 102 | 2.47 | ||||
The results from Table 1 show that the reaction is reproducible and produces stoichiometric quantities of hydrogen gas. The 102% average yield of hydrogen gas is considered to be within the measurement uncertainty; however, there are at least two factors which might have contributed to a slightly higher hydrogen yield. Firstly, the volume of gas produced was corrected to STP. It is possible that the exhausted fume hood in which the experiments were carried out could have lowered the reaction pressure below the atmospheric pressure of 758 mm of Hg. This would have increased the observed value for the volume of gas produced. An exhaust bench typically runs at 1 inch or 2 inches of water pressure. At a maximum, this could have increased the measured volume by about 0.5%.
Secondly, the water used was tap water in all cases, in which dissolved air may have been present. If any of this air had been released in the presence of the warm hydrogen gas, this would have increased the volume of gas; measured. This would have affected the results by less than 1%. Since the results are within the measurement error, and quantification of these two sources of error would not significantly affect the results, no further experiment was carried out in this area.
The procedure used in the above experiments was repeated, with the exception that the tube leading from the top of the reaction bottle was connected to a gas sampling bag. Two samples of gas were obtained and, analysed. The results are presented in Table 2.
| TABLE 2 | |||
| Gas Analysis | |||
| Hydrogen | Oxygen & | ||
| Sample | Concentration | Nitrogen | |
| 1 (1-9) | 92% | balance | |
| 2 (1-10) | 98% | balance | |
Table 2 shows that the purity of the hydrogen collected in the second sample was 98%. This is close to what was theoretically expected. The lower 92% concentration observed in the first sample was probably due to the fact the system was not completely purged with hydrogen before the sample was taken. By the time the second sample was taken, most of the air had been purged from the tube and the reaction bottle.
The procedure used in the first mentioned experiments was repeated except that the reaction bottle was placed in a water bath before the aluminum was added to the water, and the hydrogen produced was bubbled through the bath water. The temperature of the bath and the catalytic solution were measured before and after the reaction, and at about four minutes after the reaction was completed.
The water equivalent of the plastic containers for absorbing heat and their specific heat were determined experimentally by adding a known quantity of hot water to the reaction system at room temperature and then calculating the heat transfer based on the final temperature.
The quantity of heat produced by the reaction was determined and compared with the theoretical values. The results are shown in Table 3.
| TABLE 3 | ||||||
| Heat of the Reaction | ||||||
| Temp. | ||||||
| Temp. ° C. | Temp. ° C. | Temp. ° C. | ° C. | |||
| Reactor | Bath | Reactor | Bath | |||
| Readings | Start | Start | Finish | Finish | Time | |
| 1 (1-11) | 21.1 | 20.2 | 45.5 | 24.4 | 5.29 | |
| 2 (1-11) | 21.1 | 20.2 | 38.3 | 25.3 | 5.33 | |
| Heat | ||||||
| Heats of | Heat of | Heat | Output | |||
| Formation | Formation | Output | Theo- | Effi- | ||
| Al | Al | H | Actual | retical | ciency | |
| Readings | (g) | kcal/mole | kcal/mole | kcal | kcal | (%) |
| 1 (1-11) | 9.52 | −400.5 | −68.3 | 33.3 | 34.5 | 96 |
| 2 (1-11) | 9.52 | −400.5 | −68.3 | 32.5 | 34.5 | 94 |
The results in Table 3 show that the observed heat released in the production of hydrogen was 96% of the theoretical value. The 94% value from the second reading can be attributed to the heat lost to the surroundings during the time that lapsed between the readings.
The reaction has a net maximum heat production during hydrogen generation of 195.6 kCal/mole. A further 204.9 kCal/mole will be released if the hydrogen is burned with oxygen. Stated another way, 51% of the reaction energy is used to form hydrogen gas and 49% goes into the production of heat.
With 5.00 M NaOH Alkaline Solution
Sodium hydroxide (NaOH) pellets (40.63 g) from Wiler Fine Chemicals were placed in a two liter Erlenmeyer flask. Tap water (200 ml) was added to the flask. The mixture was swirled and allowed to stand on the lab bench. The lab temperature was 25° C. After about an hour, aluminum (Al) foil (30.72 g) was added in two portions. The first addition of aluminum is referred to as time zero, the start of the reaction. The temperature of the vapour coming from the top of the flask was measured using a thermometer and was found to be 93° C. four minutes after the first half of the Al had been added. The flask was open to the atmosphere. The reaction was carried out for a period of 130 minutes. Additional quantities of Al and water were added at regular intervals, and the temperature was observed and recorded. The flask was swirled periodically to ensure the solution was in contact with the Al. No further NaOH was added.
During this first experiment, a total amount of 98.7 g of aluminum was added, and 650 ml of water was added to the initial volume. A graphic illustration of this Experiment 2-1 is shown in FIG.
The addition of Al to the NaOH solution resulted in the production of vapour which issued from the neck of the flask at temperatures above 90° C. Furthermore, this production of hot vapour started within a few minutes (less than 4 minutes) of the Al being added. The reaction proceeded vigorously with the addition of each charge of Al. Furthermore, even when there was a delay between charges, such as at the 36 minute and 44 minute additions, the reaction proceeded. Indeed, even when the addition of Al was delayed for 41 minutes and the reaction mixture had been allowed to cool, the reaction still proceeded vigorously (at about 128 minutes) when Al was added and the mixture was swirled.
It is to be noted that the amount of aluminum consumed in this reaction is about 3.6 times the amount predicted by the formulas (3) and (5), and about 10.8 times the amount predicted by the equation (4). These findings confirm the catalytic nature of the reaction according to the present invention.
With 4.95 M NaOH Alkaline Solution.
To tap water (100 ml) in a one liter suction flask was added NaOH pellets (20.12 g) from Willer Fine Chemicals. The mixture was swirled to aid solvation. The lab temperature was 23° C. Two thermocouples were inserted through the suction inlet on the flask. The flask was open to the atmosphere. Thermocouple
After four minutes, water (35 ml) was added to the solution. Al foil and water were added at five minutes intervals. The flask was swirled periodically. No further NaOH was added.
The reaction was monitored for about 90 minutes. During that period a total of 53.32 grams of aluminum was consumed and 350 ml of water was added to the initial quantity. The quantity of aluminum added corresponds to about 3.9 times the amount predicted by formulas (3) and (5), and about 11.8 times the amount predicted by equation (4). Again this confirms that the reaction according to the present invention proceeds according to equation (1) or (2). In this experiment, there was no occasion in which Al was added that the temperature of the vapour being emitted did not increase two to three minutes of the Al being added. A sharp drop in the temperature was observed about one minute after the addition of water. This is to be expected since the water was at room temperature (˜23° C.) and it was poured in through the top of the flask. Thus, it would cool the system momentarily.
In both Experiments 2-1 and 2-2, there was no indication that the reaction would not have proceeded indefinitely if more Al had been added. The regular addition of Al and the fact that the temperature of the vapour remained above 80° C., except when water was added, indicate that the reaction proceeded directly and no time was there a pause in the reaction to permit the regeneration of any reagent species as predicted by the formula (6).
The following Experiments 2-3 and 2-4 were carried out at temperature of 45° C. or less to determine whether the reaction would be sustainable at these temperatures. The composition of the precipitate forming in the reaction at these temperatures, as well as the composition of the gases emitted were also analysed.
Collection of Precipitate at an Early Stage of the Reaction
Sodium hydroxide (NaOH) pellets (39.92 g) from Wiler Fine Chemicals, Lot #14449, were placed in a two liter Erlenmeyer flask. Tap water (182 ml) was added to the flask. The mixture was swirled and allowed to stand on the lab bench over night. Then it was swirled again to dissolve the remaining NaOH and mix the solution. The solution was then transferred to a 400 ml beaker.
Commercial aluminum foil (24.23 g), namely Reynolds Wrap™, a Registered Trade Mark of Canadian Reynolds Metal Company, Ltd., was>weighed, folded, and cut into portions that ranged in weight from 0.5 g to 1.5 g. The beaker containing the NaOH solution was placed in a water bath which was cooled with ice cubes. Thermometers were placed in both the water bath and the beaker. Care was taken to ensure the temperature of the solution in the beaker was kept at or below about 45° C. In each case, the temperatures of the solutions were read and recorded just before the portions of Al were added. At 29, 44, and 50 minute the reaction beaker was removed from the water bath to try to keep the reaction temperature as close to 45° C. as possible.
The Al foil was added in portions over a 59 minute period. When the Al was added to the initial reaction mixture, gas bubbles were observed to form after about 45 seconds. It was noted that when gas bubbles formed on the surface of the Al, the piece of Al floated at or near the top of the reaction mixture. A small amount of fine black material was observed to float in the reaction mixture after all the Al has been dissolved. By the 44
The solution was allowed to cool to room temperature, then it was filtered through a porcelain suction funnel without any filter paper to ensure there was no un-reacted Al present in the reaction mixture which could distort the analysis of the precipitate. The cloudy, grey, viscous material which passed through the funnel was filtered using a paper towel. It was washed with tap water. The final precipitate, a light grey solid, was allowed to stand in the fume hood overnight, then a portion of it, labelled P
Collection of Precipitate at an Advanced Stage of the Reaction
A 400 ml beaker containing tap water (175 ml) in which NaOH pellets (38.11 g) had been dissolved was placed in a water bath which was cooled by ice cubes. Al foil (39.26 g) was weighed, folded and cut into portions ranging up to 2 g. Both the NaOH and the Al came from the same source as described in Experiment 2-3. The Al foil was added to the NaOH solution over a 148 minute period following the same procedure as in Experiment 2-3. Additional water, totalling 70 ml, was added in four portions during the Experiment 2-4 at the times shown in FIG.
The reaction mixture was allowed to stand in the fume hood for about two hours after the addition of the last portion of Al, by which time the mixture had stopped bubbling. Part of the mixture was then filtered through a fine plastic mesh to ensure no un-reacted Al could contaminate the sample to be analysed. The mixture which passed through the mesh was then filtered by suction using qualitative filter paper. A sample of this grey precipitate was taken without washing and labelled P
A sample of the washed precipitate was taken and labelled P
The samples taken from Experiments 2-3 and 2-4 were analysed using a JEOL-6400 Scanning Electron Microscope (SEM) equipped with a Link eXL x-ray microanalyser. An accelerating voltage of 15 kV and a probe current of 1.5 nA were employed, and spectral collection times were 200s for sample P
| TABLE 4 | ||||||
| Sample P3-1. | ||||||
| | ||||||
| SiO | n.d. | n.d. | 0.23 | 0.32 | 0.18 | |
| TiO | n.d. | n.d. | n.d. | n.d. | n.d. | |
| Al | 59.71 | 67.63 | 80.08 | 57.50 | 70.11 | |
| FeO | 0.27 | 0.28 | 0.33 | 0.30 | 0.44 | |
| MnO | n.d | n.d. | n.d. | n.d. | n.d. | |
| MgO | n.d. | n.d. | n.d. | n.d. | n.d. | |
| CaO | 0.26 | 0.28 | 0.35 | 0.41 | 0.18 | |
| Na | 0.39 | n.d. | n.d. | n.d. | n.d. | |
| K | n.d. | n.d. | n.d. | n.d. | n.d. | |
| CuO | 0.38 | 0.46 | 0.42 | 0.70 | 0.41 | |
| Total | 61.01 | 68.65 | 81.41 | 59.23 | 71.32 | |
| |
| TABLE 5 | ||||||
| Sample P4-1. | ||||||
| | ||||||
| SiO | 0.21 | 0.27 | n.d. | n.d. | n.d. | |
| TiO | n.d. | n.d. | n.d. | n.d. | n.d. | |
| Al | 63.05 | 54.87 | 62.40 | 63.02 | 74.57 | |
| FeO | 0.26 | 0.26 | n.d | 0.29 | 0.32 | |
| MnO | n.d | n.d. | n.d. | n.d. | n.d. | |
| MgO | n.d. | n.d. | n.d. | n.d. | n.d. | |
| CaO | n.d. | n.d. | n.d. | n.d. | n.d. | |
| Na | 8.03 | 11.21 | 9.46 | 4.02 | 4.25 | |
| K | n.d. | n.d. | n.d. | n.d. | n.d. | |
| CuO | n.d. | n.d. | n.d. | 0.37 | n.d. | |
| Total | 71.55 | 66.61 | 71.86 | 67.70 | 79.14 | |
| |
| TABLE 6 | ||||||
| Sample P4-2. | ||||||
| | ||||||
| SiO | n.d. | 0.29 | n.d. | n.d. | 0.22 | |
| TiO | n.d. | n.d. | n.d. | n.d. | n.d. | |
| Al | 70.96 | 72.01 | 63.77 | 69.72 | 65.80 | |
| FeO | 0.30 | 0.35 | 0.32 | 0.23 | 0.28 | |
| MnO | n.d | n.d. | n.d. | n.d. | n.d. | |
| MgO | n.d. | n.d. | n.d. | n.d. | n.d. | |
| CaO | 0.18 | 0.10 | 0.16 | n.d. | 0.14 | |
| Na | n.d. | 0.69 | n.d. | n.d. | n.d. | |
| K | n.d. | n.d. | n.d. | n.d. | n.d. | |
| CuO | 0.42 | 0.37 | 0.30 | 0.42 | 0.51 | |
| Total | 71.86 | 73.81 | 64.55 | 70.37 | 66.95 | |
| |
The results presented in Tables 4-6 show the precipitate formed does not contain sodium beyond what could reasonably be expected to be present in an impure material precipitated from a concentrated NaOH solution. In no case was the quantity of sodium in the precipitate present in amounts exceeding 1.1% of that required by the reaction products specified in equation (3), (4) or (5). Therefore it may be concluded that the precipitate formed is not Na/Al moiety, but is rather primarily an Al/Oxygen material, which may contain some hydrogen in the form of hydroxyl groups or water molecules.
The two samples collected and analysed in Experiment 2-4 show two things, namely, the washing of the precipitate with water removes significant amounts of Na; and that none of the five measurements on the unwashed precipitate showed levels of Na which exceeded more than 34% of that necessary to form the compounds given in equation (3), (4) or (5). Indeed, the average sodium content of the five measurements was less than one-fifth of that necessary to form the compounds given in equation (3), (4), or (5). This removes any possibility that the Na/Al substances as shown in equation (3), (4) or (5) was at one time present in the reaction precipitate and was subsequently changed to an aluminum/oxygen species by washing. If such were the case the Na:Al ratio from sample P
The fact that washing with water readily removes most of the sodium confirms that the sodium species present is water soluble as would be expected for an ionic species containing sodium.
Activeness of the Filtrate
To a small amount (˜50 ml) of the filtrate from the first filtration in Experiment 2-4, was added Al foil (0.5 g). Within about 60 seconds, bubbling started and the Al completely dissolved, and a grey precipitate formed in this previously clear solution.
Collection of Gases.
To tap water (182 ml) in a four liter plastic bottle was added NaOH pellets (40.15 g). The bottle was covered, shaken and-the solution allowed to come to room temperature after the NaOH had dissolved. The bottle was then placed in a water bath at 18° C. Al foil (14.8 g) was added in three portions of about 5 g each. Both the Al and NaOH came from the same source as described in Experiment 2-3. After the first portion of Al (4.63 g) was added, the bottle was capped with a lid fitted with a hose. Bubbles started to form on the surface of the Al after about 10 seconds. Bubbles came out of the hose, which was submerged in the water bath, after about 40 seconds. The Al had completely reacted within about three minutes. The lid was removed from the bottle and a second portion of Al foil (4.98 g) was added and the bottle recapped. Bubbling from the hose started after about 30 seconds, the hose was connected to a gas sampling bag and sample P
| TABLE 7 | |||||
| Gas Analysis. | |||||
| Observed | Normalized | ||||
| Concentrations | Concentrations | ||||
| Sample # | P6-1 | P6-2 | P6-1 | P6-2 | |
| Oxygen | 2% | 1% | 2% | 1% | |
| Nitrogen | 7% | 2% | 7% | 2% | |
| Hydrogen | 86% | 92% | 91% | 97% | |
| Total | 95% | 95% | 100% | 100% | |
A series of fifteen experiments was carried out using NaOH concentrations which ranged from about 0.25M to a saturated solution of NaOH in water at room temperature. The saturated solution was about 19M. Thirteen of these experiments were recorded on graphs, and are shown in the accompanying
Solutions of NaOH were typically cooled before starting the reactions. The starting temperature for each reaction was often in the range of 4-10° C. The reactions were carried out in glass vessels ranging in size from 25 ml to 500 ml. Solutions of NaOH were prepared by dissolving NaOH pellets from BDH Inc., Toronto, Ontario, Canada, M8Z 1K5, Lot #128142-125228, in tap water at room temperature. The heat of solvation was allowed to dissipate and the portion of the solution to be used in the experiment was cooled in an ice bath in the reaction vessel.
A thermocouple junction was placed in the solution about one centimeter below the surface. The thermocouple reading was monitored continually and recorded on a computer file every 15 seconds.
Aluminum foil (Reynolds Wrap from Canadian Reynolds Metals Company Ltd., Montreal, Toronto, Calgary, Canada) was crumpled or folded and added in portions ranging from 0.2 g to 1.1 g. Each portion of Al foil was initially submerged in the solution using a glass stirring rod. Then it was allowed to float to the top of the solution. The start time for every experiment was the time when the first aluminum was added. Aluminum was added in amounts to keep the temperature above 60° C.
Water was added in amounts up to 20 ml. Water was only added when the reaction mixture became viscous and foamed more than one centimeter. In most of the experiments, the addition of water started after about 75% of the stoichiometric amount of Al was added. Water was added in sufficient quantities to ensure that the level of the solution was at least one centimeter above the level of the precipitate. In most cases, water was added only after the temperature had reached a peak or a value of at least 75° C. The portions of water were also controlled so that the temperature of the top of the solution did not drop more than 60° C. when the water was added. Aluminum and water were added until at least two times the stoichiometric amount, based on equation (3), had been reached.
After the reaction had ceased the solution was cooled and the precipitate was suction-filtered, and rinsed while still in the suction funnel with about 250 ml of tap water. Samples from the Experiments 3-1 to 3-15 were sent for elemental analysis of the precipitate and the hydrogen gas. The results of these analyses are shown in Table 8.
| TABLE 8 | |||||
| Catalytic Ratios and Product Analysis. | |||||
| [NaOH] | Catalytic | [Al | [Na | H | |
| Test (#) | (M) | Ratio | (%) | (%) | (%) |
| 3-1 | 0.26 | 3.0 | 98.3 | <0.71 | |
| 3-2 | 0.60 | 3.1 | 98.9 | <0.71 | |
| 3-3 | 1.2 | 4.2 | 96.3 | 1.14 | |
| 3-4 | 2.5 | 3.3 | 98.7 | 0.7 | |
| 3-5 | 3.9 | 3.9 | 96.8 | <0.71 | |
| 3-6 | 4.8 | 3.4 | |||
| 3-7 | 5.5 | 4.5 | 98.6 | <0.71 | |
| 3-8 | 6.0 | 2.6 | |||
| 3-9 | 6.0 | 3.3 | 98.6 | <0.71 | 97 |
| 3-10 | 6.1 | 4.2 | |||
| 3-11 | 6.1 | 3.2 | 99.3 | <0.71 | |
| 3-12 | 6.1 | 3.8 | 98.3 | <0.71 | |
| 3-13 | 6.7 | 3.3 | 99.1 | <0.71 | |
| 3-14 | 11.3 | 2.7 | 97.3 | <0.71 | 98 |
| 3-15 | 19 | 2.7 | 99.1 | 0.79 | 97 |
The expression “catalytic ratio” in the above table is calculated by dividing the amount of Al that actually reacted by the amount that would have reacted if the reaction were stoichiometric with respect to NaOH as in equation (3), (4) or (5).
Table 8 also shows the results of the analyses of the precipitates filtered from twelve of the experiments. In every case the concentration of the Al species is larger than 96%. Sodium was detectable in only three of the samples, and then at a maximum concentration of only 1.14% or less. Thus, aluminum is present in the precipitate at levels that are two orders of magnitude above sodium.
It may be concluded that the reaction according to the present invention is catalytic in aqueous solutions from 0.26 M NaOH to 19 M NaOH. It should be noted that although the 0.26 M and 0.60 M solutions showed a catalytic reaction, the reaction temperature did not rise above 30° C. during those experiments. However,
The results in
It was found that at about 75% of the stoichiometric amount the solution would become viscous and foaming with large longer-lasting bubbles. Water was added at this point and often the addition of Al had to be slowed down or an excess of un-reacted aluminum could be observed.
The formation of a greyish-white precipitate would start between 75% and 100% of the stoichiometric amount. Once the precipitate started to form it was necessary to keep the reaction zone above the precipitate a distance of about I cm, or the precipitate would mix with the bubbling aluminum and form a more viscous foam which on occasion overflowed the reaction vessel.
Based on all the experiments described herein, it will be appreciated that the present process to produce hydrogen is reproducible with aqueous solutions from 1.2 M NaOH to 19 M NaOH and over a temperature range from 4° C. to greater than 170° C. Furthermore, the reaction is catalytic over the same temperature range and over a NaOH concentration range of 0.26 M to above 19 M. The reaction's by-product comprises high-purity alumina (Al
Referring now to the graph in
Referring now the
If someone is led to believe that the reaction proceeds as in equation (3), (4) or (5), that person would logically add NaOH into the reaction vessel with the makeup water. If NaOH is added to a reaction that actually proceeds according to equation (1) or (2), however, the resulting NaOH concentration of the aqueous solution in the reaction vessel would increase as represented by curve
Reference is made again to the curve
The arrows
It has been found that the reaction proceeds better when water is added after an initial amount of aluminum has been consumed. This phenomenon can also be explained using the curve
Additional experiments were carried out using aluminum wire of different gauge sizes and aluminum flakes from the helical casing of armoured electrical wire. Although these additional experiments were not recorded in details, the catalytic effect was observed. Therefore, it is believed that the reaction (1) or (2) is reproducible with aluminum flakes from beverage cans and food packages, aluminum chips, shavings and sawdust found in machine shop waste, and aluminum powder available commercially for different purposes including fireworks, or other small aluminum particles of the like. It is to be expected that the intensity of the reaction depends upon the surface of contact between the aluminum and water. Aluminum foil for example reacts faster than a heavy gauge aluminum wire, and aluminum powder would react almost instantly to produce hydrogen gas.
A preferred hydrogen generator
A water bottle
While the distance ‘H’ of the reaction zone ‘F’ above the precipitate
Aluminum particles
The drop pipe
The aluminum particles
When relatively dense aluminum particles are used, it is recommended to install a floating screen
As to other manner of usage and operation of the process according to the present invention, the same should be apparent from the above description and accompanying drawings, and accordingly further discussion relative to these aspects is deemed unnecessary.